Thiourea derivatives having pesticidal activity

ABSTRACT

Compounds of the formula I and II ##STR1## wherein R 1 , R 2  and R 3  independently of one another are each hydrogen, C 1  -C 4  -alkyl, methoxy, halogen, trifluoromethyl or nitro, R 4  is hydrogen or methyl, R 5  is C 1  -C 3  -alkyl, R 6  is C 1  -C 6  -alkyl, C 2  -C 6  -aklenyl, C 3  -C 5  -alkynyl, C 3  -C 6  -cycloalkyl, C 2  -C 4  -(alkoxyalkyl) or C 2  -C 4  -(alkylthioalkyl), and R 7  is C 1  -C 12  -alkyl, C 3  -C 5  -alkenyl or C 3  -C 8  -cycloalkyl, and the acid addition salts of compounds of the formulae I, are novel. The compounds of the formula II can be used as starting materials for producing compounds of the formula I. The mentioned compounds of the formulae I and II have a pesticidal action, especially an acaricidal and insecticidal action, and are particularly effective against plant pest

This is a continuation of application Ser. No. 164,375 filed on June 30,1980, now abandoned.

The present invention relates to novel thiourea derivatives havingpesticidal activity, to processes for producing them, to pesticidalcompositions which contain these compounds as active ingredients, and toprocesses for combating pests by application of the novel compounds.

N-Phenyl-N'-alkyl-S-alkyl-isothioureas having pesticidal properties areknown (cp. German Offenlegungsschrift No. 2,730,620). There are providedby the present invention novel thiourea derivatives which are highlyeffective against pests, particularly against representatives of theorder Acarina, and against insects, and which, by virtue of theiradvantageous biological properties, are especially suitable forpractical application.

The novel substituted N-phenoxyphenyl-isothioureas provided by theinvention correspond to the formula I ##STR2## wherein R₁, R₂ and R₃independently of one another are each hydrogen, C₁ -C₄ -alkyl, methoxy,halogen, trifluoromethyl or nitro, R₄ is hydrogen or methyl, R₅ is C₁-C₃ -alkyl, R₆ is C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₅ -alkynyl, C₃-C₆ -cycloalkyl, C₂ -C₄ -(alkoxyalkyl) or C₂ -C₄ -(alkylthioalkyl), andR₇ is C₁ -C₁₂ -alkyl, C₃ -C₅ -alkenyl or C₃ -C₈ -cycloalkyl.

Alkyl or alkenyl and alkynyl groups in the formula I can bebranched-chain or straight-chain. By "halogen" are meant chlorine,fluorine, bromine and iodine, preferably chlorine.

The compounds of the formula I can occur in the form of addition saltsof inorganic or organic acids, and can be used according to theinvention also in the form of their salts. The term `compounds of theformula I` is accordingly to be understood as embracing within the scopeof the present invention both the free compounds of the formula I andthe acid addition salts thereof.

The compounds of the formula I can be converted into their acid additionsalts by procedures known per se. Suitable for forming addition saltsare for example: hydrochloric acid, hydrobromic acid, hydriodic acid,nitric acid, phosphoric acid, sulfuric acid, acetic acid, propionicacid, butyric acid, valeric acid, oxalic acid, malonic acid, succinicacid, malic acid, maleic acid, fumaric acid, lactic acid, tartaric acid,citric acid, benzoic acid, phthalic acid, cinnamic acid and salicyclicacid.

The compounds of the formula I are produced analogous to knownprocesses, which comprises for example reacting a thiourea of theformula II ##STR3## with a halide of the formula III

    R.sub.6 --Hal                                              (III),

the radicals R₁ to R₇ in the formulae II and III having the meaningsalready defined under the formula I, and "Hal" denoting a halogen atom,particularly a chlorine or bromine atom.

The above process is performed advantageously at a temperature ofbetween 0° and 100° C., under normal or slightly elevated pressure, andpreferably in the presence of a solvent or diluent inert to thereactants. Suitable solvents or diluents are for example: ethers andethereal compounds, such as diethyl ether, diisopropyl ether, dioxaneand tetrahydrofuran; aromatic hydrocarbons, such as benzene, toluene andxylenes; ketones, such as acetone, methyl ethyl ketone andcyclohexanone; alcohols and dimethylformamide.

The compounds of the formula II to be used as starting materials for theprocess described in the foregoing are novel and likewise form subjectmatter of the invention. They can be readily obtained from knownprecursors by reacting for example an isothiocyanate of the formula IV##STR4## with an amine of the formula V

    R.sub.7 --NH.sub.2                                         (V),

where R₁ to R₅ inclusive and R₇ in the formulae IV and V have themeanings already defined.

The process for producing compounds of the formula II is preferablyperformed is the presence of a solvent or diluent inert to thereactants, at a reaction temperature of 0° to 100° C. under normalpressure. Solvents and diluents suitable for this process are thesubstances already mentioned for the process for producing compounds ofthe formula I.

It has now been found that surprisingly the compounds of the formulae Iand II according to the invention exhibit a particularly strong actionagainst acarids which damage plants (mites: for example of the families:Tetranychidae, Tarsonemidae, Eriophydae, Tyroglyphidae andGlycyphagidae), and also against ectoparasitic acarids (mites and ticks;for example of the families: Ixodidae, Argasidae, Sarcoptidae andDermanyssidae), which infest productive animals. Some of the compoundsaccording to the invention are distinguished by a goodacaricidal-ovicidal activity and leaf-penetration action. The compoundsaccording to the invention are suitable in particular for combating thefollowing species of mites which infest fruit and vegetable crops:Tetranychus urticae, Tetranychus cinnabarinus, Panonychus ulmi, Bryobiarubrioculus, Panonychus citri, Eriophyes pyri, Eriophyes ribis,Eriophyes vitis, Tarsomemus pallidus, Phyllocoptes vitis andPhyllocoptura oleivora.

Furthermore, it has been established that the compounds of the formulaeI and II also have marked insecticidal properties, and accordingly areparticularly suitable for combating plant-damaging and ectoparasiticinsects, for example of the orders: Lepidoptera, Coleoptera,Heteroptera, Diptera, Orthoptera and Homoptera. The compounds accordingto the invention are especially suitable for combating aphids and otherinsects which damage plants by eating in crops of ornamental plants andproductive plants, for example Spodoptera littoralis and Heliothisvirescens.

Compounds of the formulae I and II according to the invention which arepreferred on account of their effectiveness are those wherein R₁ and R₂independently of one another are each hydrogen, methyl, chlorine,trifluoromethyl, methoxy or nitro, R₃ is hydrogen, R₄ is hydrogen ormethyl, and R₅ is methyl. Of importance are also those compounds of theformulae I and II wherein R₂ is hydrogen or chlorine, and also those inwhich the radical R₁ is in the 4-position. To be emphasised by virtue oftheir good pesticidal action are moreover the compounds of the formulaeI and II which are characterised in that R₇ is C₁ -C₄ -alkyl, preferablytert-butyl. Also preferred are compounds of the formula I wherein R₆ isC₁ -C₄ -alkyl, preferably methyl or ethyl.

The compounds of the formulae I and II are used according to theinvention on their own, or they form an active component in compositionswhich contain also suitable customary carriers or additives, or mixturesof substances of this kind. Suitable carriers and additives can be solidor liquid and they correspond to the substances common in formulationpractice, such as natural or regenerated substances, solvents,dispersing agents, wetting agents, adhesives, thickeners, binders and/orfertilisers.

The insecticidal and acaricidal action of the compositions according tothe invention can be considerably broadened by the addition of otheracaricides and/or insecticides. Suitable additives are for example:organic phosphorus compounds; nitrophenols and derivatives thereof;formamidines; ureas; pyrethrin-like compounds; and carbamates andchlorinated hydrocarbons.

The compositions according to the invention can be in the form of dusts,granulates, dispersions, solutions and suspensions, as well as in theform of water-dispersible wettable powders, pastes, emulsions andemulsion concentrates, and can be applied in this form.

The content of active substance (compounds of the formula I or II) inthe compositions described above is between 0.1 and 95%; it is to bementioned in this respect that with application from an aeroplane, or bymeans of other suitable application devices, also higher concentrationscan be used.

The compounds of the formula I can be formulated for example as follows:

EMULSION CONCENTRATE I

20 parts by weight of the active substance are dissolved in

70 parts by weight of xylene, and to the solution are added

10 parts by weight of an emulsifying agent consisting of a mixture of anarylphenylpolyglycol ether and the calcium salt ofdodecylbenzenesulfonic acid.

Water can be added in any proportion to the emulsion concentrate to forma milky emulsion.

EMULSION CONCENTRATE II

5 to a maximum of 30 parts by weight of active substance are dissolvedat room temperature with stirring in

30 parts by weight of dibutylphthalate,

10 parts by weight of Solvent 200 (low-viscous, highly aromaticpetroleum distillate),

15 to 35 parts by weight of Dutrex 238 FC (viscous highly aromaticpetroleum distillate), and to the solution are added

10 parts by weight of an emulsifier mixture consisting of castor-oilpolyglycol ether and the calcium salt of dodecylbenzenesulfonic acid.

The emulsion concentrate thus obtained produces milky emulsions whenwater is added.

WETTABLE POWDER

5 to 30 parts by weight of the active substance are thoroughly mixed, ina mixing apparatus, with

5 parts by weight of an absorbing carrier material (Kieselsaure K 320[silicic acid] or Wessalon S) and

55 to 80 parts by weight of a carrier material (bolus alba or Kaolin B24) and a dispersing agent mixture consisting of

5 parts by weight of a sodium lauryl sulfonate and

5 parts by weight of an alkyl-aryl-polyglycol ether.

This mixture is ground to 5-15 μm in a dowelled disc mill or air-jetmill. A good suspension is obtained by adding water to the wettablepowder produced in this manner.

DUST

5 parts by weight of the finely ground active substance are thoroughlymixed with

2 parts by weight of a precipitated silicic acid and

93 parts by weight of talc.

POUR-ON-SOLUTION

    ______________________________________                                        active substance     30.0 g                                                   sodium dioctylsulfosuccinate                                                                       3.0 g                                                    benzyl alcohol       48.0 g                                                   peanut oil           19.8 g                                                                        100.8 g = 100 ml                                         ______________________________________                                    

The active substance is dissolved in the benzyl alcohol with stirringand if necessary with gentle heating. The sodium dioctylsulfosuccinateand peanut oil are added to the solution, and are dissolved with heatingand thorough stirring.

The Examples which follow serve to further illustrate the invention.

EXAMPLE 1 Production ofN-2,6-dimethyl-4-(4'-trifluoromethylphenoxy)-phenyl-N'-tert-butyl-S-methyl-isothiourea

3.1 g of methyl iodide are slowly added dropwise, at a temperature of50° C., to a solution of 7.3 g ofN-2,6-dimethyl-4-(4'-trifluoromethylphenoxy)-phenyl-N'-tert-butylthioureain 25 ml of dimethylformamide, and the reaction mixture is subsequentlystirred for 6 hours at room temperature. The clear yellow reactionsolution obtained is stirred into a solution of 300 ml of water and 50ml of 15% sodium carbonate solution, and the oily precipitate isextracted with methylene chloride. The organic phase is washed withwater, dried over Na₂ SO₄, concentrated by evaporation, and the residueis dried under high vacuum.

There is obtained in this manner the title compound of the formula##STR5## in the form of white crystals having a melting point of 68°-70°C.

The following compounds of the formula I are produced by a processanalogous to the described process:

    __________________________________________________________________________    R.sub.1                                                                           R.sub.2                                                                           R.sub.3                                                                         R.sub.4                                                                              R.sub.5                                                                              R.sub.6   R.sub.7   Physical data                     __________________________________________________________________________    H   H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       n.sub.D.sup.20 = 1,5832           H   H   H CH.sub.3                                                                             CH.sub.3                                                                             nC.sub.4 H.sub.9                                                                        C(CH.sub.3).sub.3                                                                       n.sub.D.sup.20 = 1,5681           H   H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  CH(CH.sub.3).sub.2                                                                      n.sub.D.sup.20 = 1,5910           H   H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  CH.sub.3  m.p. 65-67° C.             H   H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       .sup.(1) m.p. (decomp.)                                                       183° C.                    H   H   H CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                         C(CH.sub.3).sub.3                                                                       m.p. 71-73° C.             H   H   H CH.sub.3                                                                             CH.sub.3                                                                             nC.sub.3 H.sub.7                                                                        C(CH.sub.3).sub.3                                                                       m.p. 67-69°  C.            H   H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                                 ##STR6## m.p. 58-60° C.             4-CH.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       m.p. 103-104° C.           4-OCH.sub.3                                                                       H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       m.p. 84-85° C.             4-OCH.sub.3                                                                       H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  CH(CH.sub.3).sub.2                                                                      m.p. 55-57° C.             4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       m.p. 95-97° C.             4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                         C(CH.sub.3).sub.3                                                                       m.p. 79-80° C.             4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                         C(CH.sub.3).sub.3                                                                       .sup.(1) m.p. (decomp.)                                                       178-179° C.                4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             nC.sub.3 H.sub.7                                                                        C(CH.sub.3).sub.3                                                                       m.p. 46-48° C.             4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             nC.sub.4 H.sub.9                                                                        C(CH.sub.3).sub.3                                                                       n.sub.D.sup.20 = 1,5725           4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             nC.sub.6 H.sub.13                                                                       C(CH.sub.3).sub.3                                                                       n.sub.D.sup.20 = 1,5639           4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  CH(CH.sub.3).sub.2                                                                      n.sub.D.sup.20 = 1,5730           4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                         CH(CH.sub.3).sub.2                                                                      n.sub.D.sup.20 = 1,5700           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       .sup.(2) m.p. 126-127°                                                 C.                                4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             nC.sub.3 H.sub.7                                                                        C(CH.sub.3).sub.3                                                                       m.p. 53-55° C.             4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                         C(CH.sub.3).sub.3                                                                       m.p. 71-72° C.             4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2CHCH.sub.2                                                                      C(CH.sub. 3).sub.3                                                                      m.p. 78-79° C.             4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2CHCH                                                                            C(CH.sub.3).sub.3                                                                       .sup.(3) m.p. (decomp.)                                                       170° C.                    4-Br                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       .sup.(1) m.p. (decomp.)                                                       187° C.                    4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  nC.sub.12 H.sub.25                                                                      n.sub.D.sup.20 = 1,5288           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       .sup.(3) m.p. (decomp.)                                                       201° C.                    4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       .sup.(4) m.p. (decomp.)                                                       183° C.                    4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  CH.sub.2C(CH.sub.3).sub.3                                                               n.sub.D.sup.20 = 1,5439           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  CH.sub.3  m.p. 36-38° C.             4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  CH.sub.2CH(CH.sub.3).sub.2                                                              n.sub.D.sup.20 = 1,5465           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  nC.sub.6 H.sub.13                                                                       n.sub.D.sup.20 = 1,5429           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                                 ##STR7## m.p. 73-74° C.             4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                                 ##STR8## n.sub.D.sup.20 = 1,5570           3-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       m.p. 77-78° C.             3-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       .sup.(4) m.p. (decomp.)                                                       143° C.                    4-Cl                                                                              3-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       m.p. 73-75° C.             4-Cl                                                                              3-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                         C(CH.sub.3).sub.3                                                                       m.p. 94-96° C.             4-Cl                                                                              3-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                                 ##STR9## n.sub.D.sup.20 = 1,5954           4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2CH(CH.sub.3).sub.2                                                              C(CH.sub.3).sub.3                                                                       m.p. 60-62° C.             4-CF.sub.3                                                                        2-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       m.p. 64-66° C.             4-CF.sub.3                                                                        2-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       .sup.(4) m.p. (decomp.)                                                       205° C.                    4-CF.sub.3                                                                        2-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                                 ##STR10##                                                                              m.p. 104-106° C.           4-NO.sub.2                                                                        2-CF.sub.3                                                                        H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                                                                       .sup.(4) m.p. (decomp.)                                                       195° C.                    4-CF.sub.3                                                                        H   H CH.sub.3                                                                             H      CH.sub.3  C(CH.sub.3).sub.3                                                                       m.p. 61-63° C.             4-CF.sub.3                                                                        H   H CH(CH.sub.3 ).sub.2                                                                  H      CH.sub.3  C(CH.sub.3).sub.3                                                                       n.sub.D.sup.20 = 1,5459           4-CF.sub.3                                                                        H   H CH(CH.sub.3).sub.2                                                                   H      CH.sub.3  C(CH.sub.3).sub.3                                                                       .sup.(1) m.p. 94-96°                                                   C.                                4-Cl                                                                              H   H CH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                   CH.sub.3  C(CH.sub.3).sub.3                                                                       m.p. 99-100° C.            4-Cl                                                                              H   H CH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                   C.sub.2 H.sub.5                                                                          ##STR11##                                                                              m.p. 86-90° C.             4-Cl                                                                              H   H CH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                   CH.sub.3  C(CH.sub.3).sub.3                                                                       n.sub.D.sup.40 = 1,5708           4-Cl                                                                              H   H CH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                   CH.sub.2CCH                                                                             C(CH.sub.3).sub.3                                                                       m.p. 90-93° C.             4-Cl                                                                              H   H CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                    C.sub.2 H.sub.5                                                                          ##STR12##                                                                              m.p. 65-70° C.             4-Cl                                                                              H   H CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                    CH.sub.3                                                                                 ##STR13##                                                                              n.sub.D.sup.40 = 1,5785           4-Cl                                                                              H   H CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                    CH.sub.2CCH                                                                             (CH.sub.3).sub.3                                                                        n.sub.D.sup.40 = 1,5698           4-Cl                                                                              H   H CH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                   CH.sub.3                                                                                 ##STR14##                                                                              n.sub.D.sup.40 = 1,5850           4-CF.sub.3                                                                        2-Cl                                                                              H CH.sub.3                                                                             H      CH.sub.3  C(CH.sub.3).sub.3                           4-CF.sub.3                                                                        2-NO.sub.2                                                                        H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.3                           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2 OCH.sub.3                                                                      C(CH.sub.3).sub.3                           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2SCH.sub.3                                                                       C(CH.sub.3).sub.3                           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  C(CH.sub.3).sub.2C.sub.2 H.sub.5            4-CF.sub.3                                                                        H   H  CH.sub.3                                                                            CH.sub.3                                                                             CH.sub.3  CH(C.sub.2 H.sub.5).sub.2                   4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  CH(CH.sub.3)C.sub.3 H.sub.7                 4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  nC.sub.8 H.sub.17                           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  CH.sub.2CHCH.sub.2                          4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                                 ##STR15##                                  4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                              ##STR16##                                                                              C(CH.sub.3).sub.3                           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                              ##STR17##                                                                              C(CH.sub.3).sub.3                           __________________________________________________________________________     .sup.(1) salt with 1 mol of HI                                                .sup.(2) salt with 1 mol of HOOCCOOH                                          -                                                                             ##STR18##                                                                    - -                                                                            ##STR19##                                                                

EXAMPLE 2 Production ofN-2,6-dimethyl-4-(4'-trifluoromethylphenoxy)-phenyl-N'-tert-butyl-thiourea(starting material for Example 1)

16.1 g of2,6-dimethyl-4-(4'-trifluoromethylphenoxy)-phenylisothiocyanate and 20 gof tert-butylamine are stirred together for 2 hours at 40° C. andsubsequently for 5 hours at room temperature. After the reactionsolution obtained has been concentrated by evaporation, the residue istaken up in methylene chloride, neutralised with ˜5% hydrochloric acidand washed with a small amount of water. After drying over sodiumsulfate, the methylene chloride solution is intensively concentrated byevaporation and caused to crystallise by the addition of hexane. Thecrystals are filtered off with suction, squeezed out and dried. In thismanner is obtained the title compound of the formula ##STR20## as a palebeige powder having a melting point of 118°-120° C.

The following compounds of the formula II are obtained in an analogousmanner:

    __________________________________________________________________________    R.sub.1                                                                           R.sub.2                                                                           R.sub.3                                                                         R.sub.4                                                                              R.sub.5                                                                              R.sub.7   Physical data                               __________________________________________________________________________    H   H   H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 161-163° C.                     H   H   H CH.sub.3                                                                             CH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                      m.p. 129-131° C.                     H   H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  m.p. 156-158° C.                     H   H   H CH.sub.3                                                                             CH.sub.3                                                                              ##STR21##                                                                              m.p. 113-114° C.                     4-CH.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 148-150° C.                     4-OCH.sub.3                                                                       H   H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 130-132° C.                     4-OCH.sub.3                                                                       H   H CH.sub.3                                                                             CH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                      m.p. 154-156° C.                     4-Cl                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 128-129° C.                     4-Cl                                                                              H   H CH.sub.3                                                                              CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                      m.p. 148-151° C.                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3  m.p. 160-162° C.                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 118-119° C.                     4-Br                                                                              H   H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 137-139° C.                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             nC.sub.12 H.sub.25                                                                      n.sub.D.sup.20 = 1,5402                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2C(CH.sub.3).sub.3                                                               m.p. 105-107° C.                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2CH(CH.sub.3).sub.2                                                              m.p. 115-116° C.                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             nC.sub.6 H.sub.13                                                                       m.p. 111-113° C.                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                              ##STR22##                                                                              m.p. 130-132° C.                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                              ##STR23##                                                                              m.p. 122-124° C.                     3-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 114-116° C.                     3-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2C(CH.sub.3).sub.3                                                               highly                                                                        viscous mass                                4-Cl                                                                              3-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 124-125° C.                     4-Cl                                                                              3-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                              ##STR24##                                                                              m.p. 97-99° C.                       4-CF.sub.3                                                                        2-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 136-137° C.                     4-CF.sub.3                                                                        2-Cl                                                                              H CH.sub.3                                                                             CH.sub.3                                                                              ##STR25##                                                                              m.p. 129-130° C.                     4-NO.sub.2                                                                        2-CF.sub.3                                                                        H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                       m.p. 135-136° C.                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             H      C(CH.sub.3).sub.3                                                                       m.p. 122-124° C.                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             H      CH.sub.3  m.p. 146-148° C.                     4-CF.sub.3                                                                        H   H CH(CH.sub.3).sub.2                                                                   H      C(CH.sub.3).sub.3                                                                       m.p. 125-127° C.                     4-CF.sub.3                                                                        H   H CH(CH.sub.3).sub.2                                                                   H      CH.sub.3  m.p. 180-182° C.                     4-CF.sub.3                                                                        H   H CH(CH.sub.3).sub.2                                                                   H                                                                                     ##STR26##                                                                              m.p. 116-118° C.                     4-Cl                                                                              H   H CH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                    ##STR27##                                                                              m.p. 143-145° C.                     4-Cl                                                                              H   H CH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                   (CH.sub.3).sub.3                                                                        m.p. 65° C.                          4-Cl                                                                              H   H CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                     ##STR28##                                                                              m.p. 56-58° C.                       4-Cl                                                                              H   H CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                    C(CH.sub.3).sub.3                                                                       m.p. 55-59° C.                       4-CF.sub.3                                                                        2-Cl                                                                              H CH.sub.3                                                                             H      C(CH.sub.3).sub.3                                     4-CF.sub.3                                                                        2-NO.sub.2                                                                        H  CH.sub.3                                                                            CH.sub.3                                                                             C(CH.sub.3).sub.3                                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.3                                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             C(CH.sub.3).sub.2C.sub.2 H.sub.5                      4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH(C.sub.2 H.sub.5).sub.2                             4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH(CH.sub.3)C.sub.3 H.sub.7                           4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             nC.sub.8 H.sub.17                                     4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2CHCH.sub.2                                    4-CF.sub.3                                                                        H   H CH.sub.3                                                                             CH.sub.3                                                                              ##STR29##                                            __________________________________________________________________________

EXAMPLE 3 Insecticidal stomach-poison action: Spodoptera littoralis,Dysdercus fasciatus and Heliothis virescens

Cotton plants were sprayed with an aqueous emulsion containing 0.05% ofthe compound to be tested (obtained from a 10% emulsifiableconcentrate).

After the drying of the coating, larvae of the species Spodopteralittoralis (L₃ -stage), Dysdercus fasciatus (L₄) and Heliothis virescens(L₃), respectively, were settled onto the plants. Two plants were usedper test compound and per test species, and an evaluation of theresulting mortality rate was made after 2, 4, 24 and 48 hours. The testwas carried out at 24° C. with 60% relative humidity.

Compounds of the formulae I and II according to Examples 1 and 2,respectively, exhibited in the above test a good action against larvaeof the species Spodoptera littoralis, Dysdercus fasciatus and Heliothisvirescens.

EXAMPLE 4 Insecticidal stomach-poison action: Leptinotarsa decemlineata

The test procedure described in Example 3 was repeated using larvae ofthe species Leptinotarsa decemlineata (L₃) and potato plants instead ofcotton plants.

Compounds of the formulae I and II according to Examples 1 and 2,respectively, exhibited in this test a good action against larvae of thespecies Leptinotarsa decemlineata.

EXAMPLE 5 Action against plant-damaging acarids: Tetranychus urticae(OP-sensitive) and Tetranychus cinnabarinus (OP-tolerant)

The primary leaves of Phaseolus vulgaris plants were infested, 16 hoursbefore the test for acaricidal action, with an infested piece of leaffrom a mass culture of Tetranychus urticae (OP-sensitive) andTetranychus cinnabarinus (OP-tolerant), respectively, (tolerance is withrespect to diazinon compatibility).

The plants infested in this manner were subsequently sprayed untildripping wet with a test solution containing 400 and 200 ppm,respectively, of the compound to be tested. An assessment was made after24 hours and again after 7 days, by examination of the imagines andlarvae (all mobile stages) under a binocular microscope, of the numberof living and dead individuals, respectively.

One plant was used per concentration and per test species. The plantswere standing in greenhouse compartments at 25° C. during the course ofthe test.

Compounds of the formulae I and II according to Examples 1 and 2,respectively, exhibited in this test a good action against Tetranychusurticae and Tetranychus cinnabarinus.

EXAMPLE 6 Action against ectoparasitic acarids (ticks): Rhipicephalusbursa (imagines and larvae), Anblyomma hebraeum (♀ imagines nymphs andlarvae) and Boophilus microplus (larvae--OP-sensitive and OP-tolerant)

The test objects used were larvae (in each case about 50), nymphs (ineach case about 25) and imagines (in each case about 10) of the tickspecies Rhipicephalus bursa, Amblyomma hebraeum and Boophilus microplus.The test insects were immersed for a short time in an aqueous emulsionor solution containing 0.1, 1.0, 10, 50 and 100 ppm, respectively, ofthe compound to be tested.

The emulsions or solutions in the test tubes were then absorbed withcotton wool, and the wetted test insects were left in the test tubestreated in this manner.

An evaluation of the mortality rate achieved at each concentration wasmade after 3 days for larvae and after 14 days for nymphs and imagines.

Compounds of the formulae I and II according to Examples 1 and 2,respectively, exhibited in this test a good action against larvae,nymphs and imagines of the species Rhipicephalus bursa and Amblyommahebraeum and also against larvae (OP-resistant and OP-sensitive) of thespecies Boophilus microplus.

EXAMPLE 7 Plant-miticidal leaf-penetration action on Tetranychuscinnabarinus and Panonychus citri

For the test were used potted bush-bean plants infested with Tetranychuscinnabarinus, and potted citrus plants infested with Panonychus citri.

The upper side of the leaves of the test plants infested with mites wassprayed with an emulsion preparation containing 400 ppm of the activesubstance to be tested. After the drying of the sprayed-on coating, theedge of the upper side of a number of infested leaves was bounded with acollar of viscous glue (Pomona Raupenleim) in order to prevent anymigration of mites from the underside to the upper side of the leaves.

The treated plants were then kept in a greenhouse at a temperature of25° to 29° C. Five days after application of the active substance, themortality rate of the postembryonal and adult stages was determined inorder to establish whether a translaminar action, that is to say, aleaf-penetrating action, of the active substance had occurred.

Compounds of the formulae I and II according to Examples 1 and 2,respectively, exhibited a good action in this test.

What is claimed is:
 1. A compound of the formula ##STR30## wherein R₁ ishydrogen, methyl, methoxy, trifluoromethyl, chlorine, bromine or nitro,andR₂ is hydrogen, chlorine, trifluoromethyl or nitro.
 2. A compoundaccording to claim 1 in which R₁ is trifluoromethyl or chlorine.
 3. Acompound according to claim 1 in which R₂ is hydrogen or chlorine.
 4. Acompound according to claim 3 in which R₁ is trifluoromethyl orchlorine.
 5. The compound according to claim 3 of the formula ##STR31##6. The compound according to claim 3 of the formula ##STR32##
 7. Thecompound according to claim 4 of the formula ##STR33##
 8. The compoundaccording to claim 4 of the formula ##STR34##
 9. The compound accordingto claim 1 of the formula ##STR35##
 10. The compound according to claim4 of the formula ##STR36##
 11. An insecticidal and acaricidalcomposition containing, as active ingredient, an insecticidally oracaricidally effective amount of a compound according to claim 1, and acarrier.
 12. A method for combatting insects and acarids which comprisesapplying thereto an insecticidally or acaricidally effective amount of acompound of the formula ##STR37## wherein each of R₁, R₂ and R₃ ishydrogen, C₁ -C₄ alkyl, methoxy, halogen, trifluoromethyl or nitro,R₄ ishydrogen or methyl, R₅ is C₁ -C₃ alkyl, and R₇ is C₁ -C₁₂ alkyl, C₃ -C₅alkenyl or C₃ -C₈ cycloalkyl.
 13. A method according to claim 12 inwhich, in the compound,each of R₁ and R₂ is hydrogen, methyl, methoxy,chlorine, trifluoromethyl or nitro, R₃ is hydrogen, R₄ is hydrogen ormethyl, and R₅ is methyl.
 14. A method according to claim 13 in which R₂is hydrogen or chlorine.
 15. A method according to claim 14 in which R₁is in the 4-position.
 16. A method according to claim 15 in which R₁ istrifluoromethyl or chlorine.
 17. A method according to claim 13 in whichR₇ is tert.-butyl.
 18. A method according to claim 12 in which spidermites and insects are combatted and in which the compound is applied toplants infested with said spider mites or insects.